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StatMech Basics II

Concepts in Materials Science I

Microcanonical Ensemble

Calculate (E, V, N )

S(E, V, N ) = kB ln

Can derive any thermodynamic potential with this

Example: Equilibrium concentration of vacancies

Example: Negative thermal expansion of polymers

Concepts in Materials Science I

Several formulae come in handy when trying to count!

For large N , ln (N !) = N ln N N ...the Sterling

approximation

R x2 p

Another, useful formula e dx =

..

Dont bother if you dont follow all the mathematical

details...just make sure that you follow the logic

Concepts in Materials Science I

It is well known that the equilibrium concentration of

vacancies in a solid scales as eEv /kB T where Ev is the

vacancy formation energy...where does this come

from?

Logic:

1. Compute entropy for a given concentration c of

vacancies S(c)

2. Compute Helmholtz free energy A(T, c) = U T S

3. Find the value of c that minimizes A, this gives the

equilibrium concentration of c

Concepts in Materials Science I

Solid thought of a collection of N atomic sites

Each site may or may not be occupied

If a site is not occupied then the system has an

additional energy...the vacancy formation energy Ev

Assume now that No sites are occupied and Nv sites

are vacant

How many microstates are possible?

Concepts in Materials Science I

N! N!

= No !Nv ! , thus, S = kB ln No !Nv !

S = N kB (c ln c + (1 c) ln (1 c))

The internal energy of the system is U = N cEv

The Helmholtz free energy

A(T, c) = U T S = N (cEv +kB T (c ln c + (1 c) ln (1 c))

A(T,c)

Taking c 1, N cEv + kB T c ln c

Equilibrium concentration c eEv /kB T

Concepts in Materials Science I

Experiment: Take a piece of rubber band, and use it

to hang a weight...gently heat the rubber band...you

will see that the weight will be lifted up!

Moral: Soft polymers contract on heating! (Why?)

Concepts in Materials Science I

Think of a polymer as a chain of N links each of

length a, total length of chain L = N a under the

action of a dead load F

The chain folds up such that the

end-to-end distance is ` (no energy cost to bend bonds)

F

`

Strategy: Calculate S, and from there G...the Gibbs

free energy (Recall, system kept at constant

pressure (force) and temperature minimizes Gibbs

free energy...

VBS/MRC Stat Mech II 7

Concepts in Materials Science I

To calculate the entropy, we need to find the number

of ways the chain of total length L = N a can have end

to end distance of ` = na (a length of a unit

polymer)

In a simple 1 D thinking, the chain is made of

segments that are pointing from left to right, and

those that are pointing from right to left

Let n = # segments from left to right, n = #

segments from right to left

N +n

Also, n + n = N and n n = n, or n = 2

and n = N 2n

N! N!

= (n )!(n )! =

( N +n

2 ) ( 2 )

! N n !

Concepts in Materials Science I

With a little algebra

kB

` `

` `

S = kB ln = 2 (1 L ) ln 1 L + L ln L

Since, bond-bending costs no energy, U = 0

G = U T S F ` =

kB T ` ` ` `

2 (1 L ) ln 1 L + L ln L F`

At a given temperature T and force F , the equilibrium

value of ` is found to be (by G/` = 0 as

2F L

` e kB T

= 2F L

L 1 + e kB T

Check limits, T 0 and T !

Concepts in Materials Science I

poly.nb

Chain Model for Polymers 1

lL

1

0.9

0.8

0.7

0.6

T kB

5 10 15 20 2 FL

Note that this effect is entirely due to entropy!

Concepts in Materials Science I

Stock Taking..

Microcanonical Ensemble: Count states, Find Entropy,

Get Any Thermodynamic Potential

This is possible only in simple cases, since

determination of can be nontrivial

Further, we always work at constant (T, V, N ) or

(T, P, N ) and therefore look to determine A or G...

Is there a direct way to get there rather than go

through S?

Yes! The Canonical Ensemble...system kept at

constant (T, V, N )! But, first some thermodynamics...

Concepts in Materials Science I

A system kept at constant (T, V, N ) will got to a state

of minimum Helmholtz free energy A = U T S

dA = dU T dS SdT = SdT P dV + dN

Thus,

A A A

= S, = P, =

T V,N

V T,N

N T,V

Also,

2A

CV = T

T 2

Concepts in Materials Science I

Canonical Ensemble

Consists of a

System + a Reservoir that make up the Universe

Energy Permiable

Membrane

E + E R = EU

V + V R = VU

N + NR = NU

System + Reservoir = Universe

System Reservoir

The Universe is microcanonical...thus system and

VBS/MRC reservoir are at the same temperature T Stat Mech II 13

Concepts in Materials Science I

Canonical Ensemble

What is the probability that the system has energy E?

(E,V,N )R (EU E,VR ,NR )

EAPP...P (E) = U (EU ,NU ,VU )

SR (EU E,VR ,NR )

Look at R closely.. R = e kB

S

SR (EU E, VR , NR ) SR (EU , VR , NR ) ( )E =

| {z } | E {z }

0

SR

1/T

0 E SR k ET

SR T, Thus, R e k e B

SR

e k 1

Since, U = const, P (E) (E, V, N )eE , = kB T

This is it!

Concepts in Materials Science I

Canonical Ensemble

The probability of a microstate with energy E of the

system is proportional to eE

We can fix the constant of proportionality...Z =

R E

R E(C)

0 (E, V, N )e = Ce dC...note that we can

convert the integral over energy to integral over all

configurations (all phase space in classical mechanics)

and thus avoid counting of states!

R E(C)

Z = Ce dC is called the Partition Function and

has all thermodynamics information!

eE(C)

P (C) = Z

How does Z give thermodynamics?

Concepts in Materials Science I

Canonical Ensemble

Energy of our system fluctuates, but the mean

energy E is the internal energy U ...That is

1

R

U = E = Z C EeE(C) dC

A bit of algebra get: U =

ln Z

U 2F

Note now that T= T T 2 ,

a bit more algebra later :

A = kB T ln Z...THIS IS THE FORMULA OF

STATMECH

Calculate partition function Z and...you are home!

Canonical advantage: Dont have to count

states...every state Cis possible with probability

eE(C)

Concepts in Materials Science I

StatMech So Far

Microcanonical Logic: Count states, Calculate entropy,

Thermodynamic functions

Canonical (T, V, N ) logic: Any microstate in this

ensemble has probability proportional to

eE ...Calculate the partition function Z and

A = kB T ln Z...everything else follows

Canonical Ensemble Example: Ideal Gas

Canonical Ensemble Example: Harmonic Oscillator

Canonical Ensemble Example: Classical Solid

Concepts in Materials Science I

Ideal Gas

N non-interacting atoms occupying a region of volume

V at temperature T (Recall, satisfies

P V = N kB T ...where does this come from?)

Main idea...in canonical ensemble any microstate C is

possible with probability eE(C)

Microstate is

(r 1 , ..., r N , p1 , ..., pN )dr 1 ...dr N dp1 ...dpN .....the energy

PN pi pi

associated is i=1 2m

Partition function

R R R R

P

N p i p i

1

Z = ~3N N ! V dr 1 ... V dr N dp1 ... dpN e i=1 2m

Simplifies to

N 3N

VN

R p2

V N

2m 2

Z = ~3N N ! e 2m dp = ~3N N !

VBS/MRC Stat Mech II 18

Concepts in Materials Science I

Ideal Gas

Internal energy U = E =

ln Z

= 32 N kB T !

Now, with

3N 2m

A = kB T N ln V N ln N + N + 2 ln ~2 , and

A N kB T

P = V , we get P = V ...Shri. Bolye rises from

microscopics!

The mean energy is U ...but what about standard

deviation? This is

2 ln Z

U = (E E) = 2 = 32 N kB

2 2 2 T 2 ...thus

U

U 1 0 as N ! Thermodynamic limit,

N

and why we see very reproducible things in

experiments with no affect of particular microstates

etc...think of the copper puzzle...it is resolved!

VBS/MRC Stat Mech II 19

Concepts in Materials Science I

What is internal energy and specific heat? (Note,

p2 m 2 2

H= 2m + 2 x )

Microstate (x, p) is possible with probability eE

Partition function Z=

p 2 m 2 2 q q

1

R R + x 1 2 2m 2

~ dx dp e 2m 2

= ~ 2

m = ~

U = E =

ln Z

= kB T ! Looks familiar!

Specific heat C = kB ...also familiar!

Concepts in Materials Science I

What is internal energy and specific heat? (Note,

pp m2

H = 2m + 2 r r)

Microstate (r, p) is possible with probability eE

R

p p m 2

2m + 2 r r

Partition function Z = ~13 drdp e =

q 3 q 3 3

1 2 2m 2

~ 3 2

m = ~

U = E =

ln Z

= 3kB T ! Looks familiar!

Specific heat C = 3kB ...also familiar!

Concepts in Materials Science I

Classical Solid

The solid (N ) atoms may be thought of as a collection

of 3N oscillators (phonons) with Hamiltonian (roughly)

P P k P k mk2

H(A1 , ..., AN , P 1 , ..., P N ) = k 2m + 2 Ak A k ,

where k (total of N ) is the wavevector of the phonon

Since these are independent oscillators, we have

Q 2 3

Z = k ~k

P P

U =

ln Z

= k 3 ln 2

~k = k 3kB T =

3N kB T

C = 3N kB , but hey, thats Dulong-Petit!

Concepts in Materials Science I

U

How do we get specific heat CV ? Well, CV = T

U 2 ln Z

CV = T = kB 2 U

= 2

kB 2

2 ln Z 1

But, 2 = U 2 , or CV = kB T 2 U 2!

result...fluctuations at equilibrium are a measure of

how system resists change of equilibrium! Related to

the more general Fluctuation-Dissipation Theorem

Concepts in Materials Science I

Summary

Canonical Logic: Calculate partition function...obtain

free energy...go home!

We have seen how StatMech helps understand

material properties...from equilibrium concentration of

vacancies, to polymers, to ideal gases etc!

Next we shall look at Quantum Statistical

Mechanics...essentially same ideas, but counting will

be different respecting type of particles...Bosons or

fermions

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